Plant growth regulation



Patented Sept. 2, 1952 Nathaniel Tischler, Palmyra, N.- assignoirstciSharples Chemicals Inc., a corporation of Dela- Ware No Drawi ngl,Application February 27, 1951, Serial No. 213,062

This invention relates tonew 'andimproved compositions of matter .Whichare used for treating growingplants to alter the normallife. cycle ofsaid plants with advantageous results. It is particularly concerned withphytotoxic compositions which contain at least one of the 3,6'-endoxohydro-orthophthalic acids as active ingradient, that is, as plantresponse agent.

Phytotoxic compositions containing at least one of the aforesaid acids,and particularly 3,6- endoxo-1,2,3,6 '1 tetrahydro-orthophthalicj acidand/or 3,6 endoxohexahydro orthophthalic acid, per se or in equivalentform, and more particularly the eXo-cis isomers, are highly efiectivefor the purpose, and it is a feature of this invention to providecompositions containing the above active ingredients in admixture withsimple, readily available materials which enhance,

or intensify the plant response activity of the above activeingredients. These and other features will become apparent to personsskilled in the art as the specification proceeds.

(Jo-pending application ,SBIiEtl'NO. 81,026, filed- March 11, 1949, byNathaniel Tischlerand Ernest P. Bell, now Patent No,;2,576,080, grantedNovember 20, 1951, teaches: the efficacy ofthe3,6-endoxohydro-orthophthalic acids and their derivatives in bringingabout useful plant response effects such as leaf abscission (partial orcomplete), blossom thinning, vine-kill, total de v struction of theplant, adventitious root formation, or delay of fruit drop, theparticular-plant,

response manifested depending to a large extent upon the appliedconcentration of .the response agent, and the species and degree ofmaturity oi the plant undergoing'tre'atment; The .use of,3,6-end'okohexahydro orthcphthalic acid, pe'r se 'or in equivalent form,for

the above purposes is particularly described and claimed in thecoepending application of Ernest P. Bell and Nathaniel 'Iischler,SerialNo. 131,501,

filed December 6, 1949, now Patent No. 2,576,08 granted November20,1951; andthe use of 3,65

endoxo-1,2,3,6-tetrahydro orthophthalic acid, per se or in equivalentform, for such purposes is particularly described'and claimed in thecopending application of the same inventors, Se

rial No. 131,502, filed December 6,1949, now Patent No. 2,576,082,granted November 20, 1951. Both of these applications arecontinuationsin-part of said first-mentioned application.

The above-mentioned compounds as applied to plants may be in the form ofthe acid per se or in other form, such as in the form of the anhydrideand/or a salt which contains the cor- 1 ,"16. cars. (01., 71-25)responding anion of, anions of ortho configuration, the same as in thecase of the acid per se, said anion or anions being either acidorneutral in character, in chemical combination with a sufiiciency ofcation or cations to satisfy valence requirementsfsuch as one or ,moremetal and] or 1 metalloidjcatio'ns such-as sodiumJp'oteisium, calcium,strontium, magnesium, aluminum, iron,

cobalt, nickel, zinc, cadmium, mercury, copper,-

ammonium, mono ii-f and trialkylammoni'um, mono-' diand vtri-alkanolammo'nium', and

mixed alkylalk'anola'mmonium which is N-sub st'ituted by from 21 to 3radicals of'the type indicated'.

Thus the acid'is'the" active material and this is'ltru'e whether it isused as such, or in the form of a salt, or anhydride, orother equivalentform. These changes at the carboxyl groups aremere changes in formratherthanlchangesin substance.

Turning now to the present invention, which for convenience 'will'bedescrib ed more particu-, larly with reference to 3,6-endoxohe'xahydro-1 orthophthalic acid and- 3,6-endoxo-,1,2",3,6-tetrahydro-orthophthalicacid (perse or in equivalent form) as active plant-response ingredientsof my new compositions, it is pointed out that said-acids areappreciably soluble inwater; The other forms' are also water-so1uble.Some of them are highly soluble, while-others have a lesser degree ofsolubility Howeverpit islpreferred to employ compounds having asolubility,

in water to the extent of at least 0.1% by weight,

and still more particularly .of at 'least l% by Water solubility isdesirable scjthatanions,

(acid or neutral-or both); are formed= ;when;the

acids, perse or'in chemicallyequivalent form,, are dissolved-in water.The desirability of such.

anions will presently becom lza parent. Acid anions may be.theoretically-illustrated by reference to the acid 3,6 -endoxohexahydroorthophthalate anion, by which is meant a univalentanionhavin a structure defined by the theory to be hydrogenl Neutralanionsmay be theoreticallyillustrated by reference' to the neutral3,6-endoi'c ohexahydro-orthophthalate anion by which is meant wherein Xis a cation, consideredf'by' modern a divalent anion having a structuredefined by the formula Thus the foregoing active ingredients may bedefined as compounds which when in the presence of water yield anionshaving the configuraon I in which Y represents one of the groupconsisting o'fjanunsatisfied valence'and acation, 'a'nclin whichRjrepr'esents'one of the group consisting of the vinylen'e" radical andtheethyleneradical.

Although the present applicant does not wish to bebound, byanyjparticular theory as to the mechanismwhereby useful plant responseefiects are produced, aconsiderable'amount' of experimentation'stronglyindicates that said ffects are broughtabout'by the existence in aqueousmedia of anion or'anionsTacid and/or neutral) of the type illustratedabove; Both neutral anionand' acidanio'n arefeflective. A salientfeature of this theory is that'the'acid'or acids of the invention, whenapplied per se, or in equivalent form, to a living plant, makes thedesired anion or anions (acid and/or neutral)' 'available to the plant,at or" nearthe site' of application," and through tra'nslocationphenomena; at points from the site of application;

The desired anion or anions are made available by virtueofthe fact thatthe acids per se, and their equivalent forms; ardwater-soluble andioniz'able; Therefofa'whensiich a compound is absorbed into the vascularsystem of a' plant; it'

dissolves in the aqueous plant juices and'p'rovides theffunctioninganion oranions. The resulting physiological activi'ty is believed to beascribable to the pi'esence of} said anion'or' anions. The acids per seand'their equivalent forms may thus y be regarded as very convenientmedia for furnishing-the desired anion or anions lac-susceptibleportions ofthe plant;

It follows, thereforathat the acids per se and ammonium and substitutedammonium "salts of unsubstituted, open-chain, carbon to carboni linked,dicarboxylic and tricarboxylic acids having no greater unsaturation thana single olefinic linkage and having from 2 to 6 carbon atoms; saidsalts being either in neutral or acid form. Particular substitutedammonium salts are the alkylammonium salts, alkanolammonium salts, andmixed alkylalkanolaminonium salts By the term carbon-to-carbon linked"is meant that carbon atom. I

each carb'on atom 'is' linked toatileast one other far removed Examplesof such unsubstituted, open-chain carbon-to-carbon linked dicarboxylicand tricarboxylic acids having no greater unsaturation than a singleolefinic linkage and having from 2 to 6 carbon atoms are oxalic,malonic, succim'c, glu- =taric, adipic, tricarballylic, maleic, fumaric,aconitic, alpha-hydromuconic acid, beta-hydromuconic, pyrotartaric,ethylsuccinic, -alpha,alphadimethylsuccinic, alpha,betadimethylsuccinic, alpha-methylglutaric, beta-methylglutaric,methylmalonic, ethylmalonic, dimethylfumaric, citraconic, mesaconic, anditaconic acids.

Examples of salts of such acids are ammonium salts, including neutralammonium salts, as well as ammonium acidsalts such as of thedicarboxylic acids, and such as diammonium hydrogen and ammoniumdihydrogen salts in the case of tricarboxylic acids; mono-, di-, andtrialkylammonium salts having from 1 to 4 carbon atoms in each alkylradical; mono-, diand trialkanolammonium salts having from 2, to 3carbon atoms in each alkanol radical; and mixed alkylalkanolammoniumsalts which are N -substituted by from 2-to 3 radicals of the type andcarbon content indicated. The substituted ammonium salts include bothneutral and acid salts, wholly analogous to'the ammonium tioned above.

In the case of salts containing more than one ammonium and/orsubstituted ammonium radicals (i. e;, cations), said'cations may be thesame or' different.

The preparation of the salts falling within the scope of the inventionmaybe accomplished by any means known to'the art, suchas by neutralization of a selected acid with the requisite amountof the selected baseor mixture of bases. In general, water is an excellent liquid medium forcarrying out such neutralizations, although 7 gest themselves to personsskilled in chemical synthesis uponbecoming familiar with the chemical"structure of such compounds.

The 'amountlof additive or intensifier to be admixedwith'the endoxocompounds may vary over a"very wide range, and even a small amount ofthe intensifier will produce a useful synergistic intensifying effect.Generally speaking, for practicable purposes, proportions of intensifierto ac tivein'gredient of from lzlllto 50:1, and par'- ticularly from 1:1'to'20jl, are very useful.

The intensifier and the active ingredientmay be admixed in anydesiredmanner such as by mere mechanical mixing in solid form, or whilein solution in a common solvent such as water. In the latter case thesolution may be marketed as such, orif desired, may bejdr'ied, such asby sprayor drum drying. man case, it is preferred toh'ave a solidadmixture in finely divided form and suificientlydry to befree'fiowi'ng.

'Thef admixtures are applied to the crop or plants in any desired'inannerfsuch as in the form a solid, for example, by dusting, or in hee mb m ms xample by spravine Compositions may be formulated by mixingthe admixture containing the intensifier and active ingredientiwith anydesired liquid or solid carrierssu ch as any of the finely divided solidcarriers known in the dusting art, which areprefer- .ablyof: largesurface area, such as clay, for exsalts such as are menample, fullersearth, pyrophyllite, talc,'=bentonite, kieselguhr, diatomaceous earth,etc.""Any of the commercial clays available on the market in finelydivided form maybe used, andparticularly those which are normallyemployed as insecticide carrie'rs. Commercial clays, it will beunderstood, are generally identified by trade names (reflecting thesource and mode of processing), of which HomerClay, Celite, andTripolimay be mentioned;

Non-clay carriers which may be formulated.

with my admixture include; for example, sulfur,

as typical.

volcanic ash, calcium carbonate, lime, by-product lignin,lignocellulose, flour, such as wood, walnut.

. Anydesired mixturemay be prepared by any shell, wheat, soybean,potato, cottonseed, etc;

mixed with the intensifier in finely divided form; in amounts smallenough to preserve1the.free,.

fiowing. .property of thefinal dust composition. Or excess liquid may.be removed. such as by vaporization, for example, under reduced.pressure. The same applies to mixtures of the active ingredient, theintensifier, and any finely dividedsolid carrier and/or other material.

When solid compositions are employed, in order to obtain a high degreeof plantcoveragewithv minimum poundage per acre, it is desirable thatthe composition be in finely divided form. Preferably, the dustcontaining the active ingredient should be sufiiciently fine thatsubstantially all will pass through a 50 mesh sieve, and moreparticularly through a 200 mesh sieve Excellent results have beenobtained in which the dust com.-.

position is comprised predominantly of particles in the range from 15 to45 microns. Finer dusts, such as those consisting largely of particlesin the range of 5 microns and below have excellent covering capacity butare somewhat more subject to drift and are more expensive to prepare.

,F'or spray application the admixture may be dissolved or dispersed in aliquid carrier such as water or other suitable liquid.

Aqueous solutions or dispersions are economical and desirable. Ingeneral, the choice of the particular liquid carrier employed will beguided somewhat by prevailing circumstances, such as its availability,its solubility or dispersion characteristics toward the particularadmixtureem ployed, and/or its toxicity toward the plants dergoingtreatment. In general, water is an excellent liquid carrier.

Thus, spray formulations comprising dispersion, or emulsion, in aqueousor nonaqueous media may be employed.

Emulsions or dispersions of the admixture in th liquid carrier may beprepared by agitation of the admixture with the carrier. This iscommonly done at the time of spraying. Preferably,- however,; theagitation should take place in thepresence of an emulsifyingordispersing; agent.-

(surface-active agent) ,inorder to facilitate the preparation of saidemulsion or dispersion. Emulsifying and dispersing agents are well knownin the art, and include, for example, fatty alcohol sulfates, such assodium. lauryl sulfate, aliphatic or aromatic sulfonates, such assulfonated .castor oilor the variousalkaryl sulfonates (such as the theactive ingredient in the form of a solution, suspension,

6 sodium salt'of monosulfonatednonyl naphthalene or tertiary "docecylbenzene), and non-ionic types of-emulsifying and dispersing agents suchas the high molecular'weight alkyl polyglycolethersor analogoustliioethers such as'the' decyl, dodecyl and tetradecyl poly'glycolethersand thioethers containing from 25 to carbon atoms The use, if desired,of adjuvants,such as wetting-agents and/or humectants(water-mammage'ntsi, is also contemplated in'connection with solutionsofthe -'admixture', such' as water solu tions.- Any suitable wettingagent and/or humectant may b employed for this purpose,

suchasthe wetting agents more particularly re ferre'd- -to above.Examples of humectants are glycerine, diethylene glycol, ethyleneglycol, poly-- ethylene glycols generally, and water-soluble sugars andsugar containing mixtures, such as glucose, fructose, galactose,mannose, arabinose, XY1OSB,$11CIOS8 maltose, lactose, railinose,treh'alos'e," dextrins-such as white dextrin, canary dextrin, Britishgum-,'-etc honey molasses, maple corn syrup, etc.

For adjuvant purposes, any desired quantity syrup, maplesugar, andstarch syrups such as 250% or more based on active ingredient. Forwetting purposes, the amount of adjuvant used may be considered to bethat required to impart th'e'desired wetting qualitiesto'the spraysolution" as formulated'such as approximately 0.05% by weight 'of the,spray. solution, The use of considerably larger amounts is not basedupon'wetting properties, although present, but is a function of thephysiological behavior of the wetting agent after spraying upon theplant.

It should be considered that .once the solution has been sprayed upontheplant, the concentration of wetting agent existing upon the plant isin no sense a function of the concentration exist-' ing in the originalspray solution. Thus, evaporation might concentrate the wetting agentconsiderably, or the presence of dew on the plant sur- 1 faces, orofplant juices on the plant surfaces might considerably dilute thisagent.

" It will, of course, be understood that wetting i agents, particularlyin solid form, may be compounded with the admixture when in solid form;Although the admixture of activeingredient .and'intensifier may beapplied to the growing plant in'concentrated form, it is usuallydesirable to employ liquid or solid formulations, for example, asdiscussed above, in which the active ingredient constitutes lessthan'30% byweight of the total, such as less than 10 and even as lowQther substances than the carrier, surface active agent, and/orhumectant may be included in solid or liquid formulations if desired.Thus, active ingredients other than those disclosed herein andcompatible with'the admixture may be ousphysiological effects. ,Forexample, it may at times be expedient toinclude'singly or incombination. substances such as fungicides, insecticides, bactericides,or types of plant-response agents other than those agents discussedherein.

"In practice of theprocess as applied to defolia-- tion, the rate ofapplication (1. e. the amount of of wetting agent may be employed, suchas-up to- Such" other active ingredients may be 7- edmixtu p r c p. or;est es swill; e end am n oth r-fact supon the. species of. P ent .-.bens treate 1 n pon their matu ty n. any v nt, mou t. f. a tive. ngredientempolq esi q t t e ame lant r smnse fiectwilt Substantia y-M ler han whn. the. intensifie is intn esent.

- A sm l he-mere me u e he mantel-i: the ime. of: stim tion. he. l ss.act ve materi l: requi ed n. r s e. he cro i prmallv; ree ed o defolia in. ur oses. weeks. ri r. to her e ne. n some. anee l more; Wartim applat n-mes d rab e-serenely. fimevv. eins. Medsfibwh cur sq ne ter. heenlistees. o. was n. eq n lative effect he ea i rastic 1 iq;p955i i in er est e t yvb @enable ex'p riene rsseter to rmyn i e il s n a l te ebel8 eate ast followltvith second application if necessary; fte e i n o i't fi e e bt iaihe deg-tee of defoliation desired. 7

Useiof dosages greatly in excessof theminimum. required for gooddefoliation may result .in shock to. the plant with. attendant injury tothe .remainder of the plant;

"In fact, the plantresponse compositions. of th e present. inventionare, effective herbicides when usedlinamounts substantiallyv greaterthan those required for defoliation, and. they; maybe usedadvantageously for the killing; of .plants} or. .vines p(as.initlie..caseof potatoes) when d$ired,; such asI, forv the killingof]'undesinecl plants. for. ex ample, weeds .or grasses, or. for thekilling of crops; irrespective for. whethersuch. undesired... plants orcrops aren t-"species whiohfllend th em: selves to defoliation;

Thus. when defoliation is. thecbjective the quantity applied should ibe,sufiicient tto. .cailse at. f w h 11194101. p t qmof thele'aves .to..dry.up and/or to drop from the living plant, but insufli cient to causesubstantial herbicidal tuitionv onthe plant On the other hand; whenplant killing is the. objective, any amount sufficientifor. this purpose may be applied. I'n. the lattenconnection, since different species.of plants .vary. markedly. in their. relative resistance to,herbicidallaction, selective killingofv plant. speciesmay be practicedrSuchselectivityf may be. varied bycompflnding, such .as with Qadjuvants, for example, wetting agents, in addition to theuseotanintensiiier,

I am aware of. the .factthat it has. vbeenproposed to usecertaimarmnonium salts, such ashnimqa niumsulfate, in combination.withlphenolic sub;-. stances, such. as dinitroallcylphenols f and pentachlorophenol, for plant response purposes; The. purpose of such use of vammonium salts ,asexplained ,by, Crafts and .Reiber, Hilgardia,,v01u1ne, 16,.pages 487-499, andby. Crafts, Science,,volume.. loflgpages85-86, isto malge availahlethe free phenol at the plant; surface froman. aqueous.v solution, of .a .watersoluble salt. of said. phenol. Theph.eno1 in, such cases is theflactive lplant sp se ubstance; and is.cont nuous y .res' n erated atthe plant surface from it s water-sold ,esalt by vi'r'tue of the presence ot the ammoruum surface, further ireephenolj enerated under q l b iu ndit n The pl nt re nseefi ct of thefreephenol is not enhanced o intensified lt-Q s the. he ebierbedb the page;

vehicle. for app1ying; the lant. response. agent;

i. e, herbicide,- to theplant; surfaces.

.Injhe .caseof, my; invention, on the. other hand; the plant; responseefiect obtained; from a. given quantityeof. active. ingredient issreaterthan that: obtained bythe applicationofthe samequantity; of..- the.particular. active. ingredient to; the plant; In, fact; the

in. the absence. ofv my intensifier. plant. response efiect; obtainedwiththesame quantity of active ingredient may be increased manystimes bythe addition of. larger quantities of; myintensifier. The.intensification begins. to. manifest itself. by. thesaddition of a.small'proportion of my intensifier and increases ..to.a.point. ofoptimum intensification by. the addition of. in-.. creasingproportionsofintensifier. Foinoptimum plant response effects, the. .prop0rti0no.intensi-. fiermtoactive ingredient may. vary somewhat bee...tweenspecific. active ingredients and between. specific, varietiesot.plants undergoing. treatment,

sol that theaexactproportion. for optimum eifectv unden all.conditionscannot .begiven. However, the 1 intensification of I theplantresponse... efiect is presentwhena small-quantity of intensifier isadded-andsthe addition oi-intensifier beyond the: pointat,- Which nofurther marked increase in ever, such intensificationis cogentlydemonstrated-by-thefollowing examples which are by way oi -illustrationand not of limitation.

EXAM J Elevemseries of "aqueous solutions of disodium3,6eendoxohexahydro-orthophthalate were prepared each seriesconsistingof five solutions havingthe following respectiveconcentrations of thisactive ingredient 0.00125 0.0025%-; (H305 0.0075and 0:01-

One series of solutions containedno intensi-- fier; Each of theother-tenseries contained-, -in

additionto the active-ingredient, a constant amount (0.05%) of an-intensifiers- The respective intensifiersemployed in preparing therespective-series ot s0lutions were ammonium acid oxalate,"ammoniumoxalate, ammonium acid malonate, ammonium-malonate; ammoniumacid succinate, ammonium succinate, ammonium acid adi-pate,ammoniumadipate ammonium dihydrogen aconita-te and.diammoniumhydrogenaconitater Thus theratio of-intensifier to activeingredient ranged from 5 1 to 40 :-1. r

These solutions-were applied to potted young Dwarf--Horticultural beanplants which wereabout 8 inches high, and on w-hiclrthefirst trifoliateleaf 7 was larg and the second trifoliate leaf -wasssmalle Separategroupsof eight such plants weredi-pped to the first-nodesinto-therespective test solutionsf each series; and the excess'solutionwas shakenoit. Approximately 2 ml. of=-s01liti0n remained on -eachplant-.- Thus thedosageper plantofactive-ingredient,-depending on therespective concentrations of the testsolutions;wereapproXimatelv'25,-50,- 150,- and Y 200; micrograms;respectively.- The dosage -per plant-of--intensifier was --consta-nt-,amounting to approximately- 1 000- micrograms.

One group on eight plants I was not; treated with 1 any-solutionfand waskept as a control.

Control tests-using the intensifiersin the absenceofinctive-ingredientwere also conducted; 'Groups of eight plants were treated with 0.05%

9 aqueous solutions of the respective intensifiers, using theabove-described method of application.

All plants used for this test were of the same Observations made fourdays later were as follows age and had been grown at the same time andPhysiological effects under the same conditions. After the test wascommenced, treated plants and untreated congr Withoutmtensifier Withammonium acid trols were again kept under the same conditions maleateand therefore were subjected to comparable grow- P t ing conditions.

Observations made three days after treatment tirettiiiijijiii i28:::::::::::::::::: trt' i'ftfr rr 'tttifit are Summarized in Table v0.005 PL-lt bn; TS-mod ret 7B i l s a a jg% mod Several symbols areemployed in this table, bn;TS-mod ret.

their meanings being as follows in this example i ggg g fig 8B;

and wherever applicable in the Other examples:

1t=1ight1y 1D EXANIPLE 3 sev=severe1y Four series of aqueous solutionsof disodium bn=bumed 3,6-endoxohexahydro-orthophthalate were pre-.

ret=retarded 2O pared, each series consisting of five solutionshavadh=adhering mg the following respective concentrations ofczuntreated Control this active ingredient: 0.001%, 0.0025%, 0.005%,

Tsztrifoliate shoots One ser es of solutions-contained no intensifier.

Each of theother three series contained, in addi-- 28, for example,means each of two plants had a single primary leaf abscised; 6B, forexample, means each of six plant-s had both primary leaves tion to theactive ingredient, a constant amount (0.05%) of an intensifier. Therespective intensifiers employed in preparing the respective seriesabscised. of solutions were methylammonium acid maleate,

TABLE 1 Physzologtcal effects ACTIVE INGREDIENT PER PLANT Intensifier 25micrograms micrograms micrograms micrograms 200 micrograms None As 0 AsO Pl-lt bn; TS-as C PL-mod bn; TS-lt ret. 4131; Saab tPL-mod bn;

, re Ammonium acid PL-lt bn; TS-as O 28; PL-mod bn; TS-lt 6B, 18; adhPL-mcd 8B; TS-sev ret 8B; TS-sev ret.

oxalate. ret. bn; TS-mod ret. Ammonium oxa- 3B, 28; adli PL-mod 3B, 38;adh PL-mod 7B; adh PL-mod bn; 7B, 1S; adh PL-mod 8B; TS-sev ret.

late. bn; TS-lt ret. bn; TS-lt ret. TS-sev ret. bn; TS-sev ret. Ammoniumacid PL-mod bn; TS-lt ret. 1B; adh PL-mod bn; 5B, 25; adh PL-mod 8B;TS-mod ret 8B; 'IS-sev ret.

malonate. TS-lt ret. bn'; TS-mod ret. v Ammonium mal- PL-lt bn; TS-as O13, 2S;adl1 PL-lt bn; 4B, 28; adh PL-mod 2B, 48; adh PL-mod 6B, 18; adhPL-mod onate. 'lS-lt ret. bn; TS-lt ret. bn; TS-mod'ret. bn; TS-sev ret.Ammonium acid Pl-lt bn; TS-as C 1B, 18; adh PL-lt bn; 2B, 38; adh PL-mod'63, 1S; adh PL-mod 6B, 28; adh PL-mod succinate. 'IS-as 0. bn; TS-modret. bn; TS-sev ret. bn; TS-sev ret. Ammonium suc- PL-lt bn; TS-as C"..-PL-ltbn; TS-1trct 1B, 45; adh PL-mod 3B, 28; adh PL-mod 7B, 18; adhPL-mod oinate. bn; 'IS-lt ret. bn; TS-mod ret. bn; TS-sev ret. Ammoniumacid PL-lt bn; TS-as 0.... 1S; adh PL-lt bn; TS- 4B, 23; adh PL-mod 6B,18; adh PL-mod 8B; TS-scv ret.

adipate. ret. bn; TS-mod ret. bn; 'IS-mod ret. Ammonium adi- As O 3B;adh PL-lt bn; 4B, 18; adh PL-mod 7B; adh- PL-mod bn; 7B, 18; adh PL-modpate. 'IS-lt ret. bn; TS-mod ret. TS-mod ret. 7 bn; TS-sev ret. Ammoniumdihy- PL lt bn; TS-as C i 1B, 28; adh PL-lt bu; 5B; adh PL-mod bn; 4B,18; adh PL-mod 7B, 18; adh PL-mod drogen aconitate. S-lt re TS-1t ret.bn; TS-mod ret. bn; TS-mod ret. Diammonium hy- PL-lt bn; TS-as O...PL-mod bn; TS-mod 6B, 13; adh PL-mod 5B, 18; adh PL-mod 8B; 'lS-mod ret.

drogen aconitate. ret. bn; TS-mod ret. bn; TS-mod ret.

Those plants which were not treated and those methylammonium acidsuccinate, and methylammonium acid malonate.

plants which were treated only withthe intensifiers were entirelyunafi'ected. Similar control tests were conducted in the succeedingexamples,

and in no case was any effect noted on-the plants.

EXAMPLE 2 Two series of, aqueous solutions of disodium lowingconcentrations of active ingredient: plant of active ingredient,depending on the 0.0012575, 0,0025%, 0.005%, and 0.'0075%. respectiveconcentrations of the test solutions,

Thus the ratio of intensifier to active ingree were approximately 20,50, 100, 200, and 300 dient ranged from 6.6:1 to 40:1. micrograms,respectively. The dosage per plant Separate groups of eight potted DwarfHortiof intensifier was constant, amounting to approxcultural beanplants at the stage at which the v imately 1000 micrograms.

firsttrifoliate leaf was still furled were dipped to the first nodesinto the respective test solutions of each series, and the excesssolution was shaken off. All groups were grown at the same time andunder the same conditions.

Thus the ratio of intensifier to active ingredient ranged from 3.3 :1 to50:1.

Separate groups of eight potted Dwarf Horti-.

cultural bean plants at the stage at which the first trifoliate leaf wasstill furled weredipped to the first nodes into the respective testsolutions of each series, and excess solution was shaken off.Approximately 2 mlof solution remained on each plant. Thus the dosagesper All plants used for this test were of the same age and had beengrownat the same time under the same conditions. After the test wascommenced, treated plants, including the treated controls, and theuntreated controls were again kept 11 under the same conditions and.therefore. were subjected to comparable growing conditions. Observationswere made four days after treatment, with results as summarized in Table2.

TABLE 2 Physiological efiects ACTIVE INGREDIENT PER PLANT Intensifier 20micrograms 50 micrograms 100 micrograms 200 micrograms 300 microgramsNone As O .4 As O 413, IS; aeih PL-mod 6B, 18; adh ILL-mod 6B, 23; adhPL-frozen,

I bu; 'Icr bn; TS-mod ret. TS-mod rct. Methylammo PL-lt bn; 'IS-lt ret2S; adh PL-mod bn; 5B; adh PL-mod bn; 7B,1S;adh PL-irczen; 8B; 'lS-scvret.

niuin acid male- TS-lt ret. TS-mod ret. TS-scv ret. ate. M ethylammo-PL-lt bn; TS-as 4B, 28; adh PL-lt bn; 4B, 25; adh PL-mod B, 28; adhPL-frczen; 4B, 28; adh-PL-frozen;

nium acid succi- TS-mod ret. bn; TS-mod ret. 'lS-sev rct. '1Ssev rot.nate. i Methylammo- PI -lt bn; TS-mod ret. 2B, 28; adh PIi-lt bn; 4B,35; adh PL-mod 7B, 1S;adhPL-frozen; 1B, 68; adh -PL-Irozcn;

nium acid malo- TS-mod ret. bn; TS-mod ret. TS-sev rct. TS-scv rot:hate.

it is to be understood that freezing of leaves indicates a morephytotoxic condition than when the leaves actually abscise.

dosage per plant of intensifier was constant,v

amounting to approximately 1000 micrograms.

All plants used for this test were of the same age and had been grown atthe same time'under the same conditions. After the test was commenced,treated plants, including the treated controls, and the untreatedcontrols were again kept under the same conditions, and therefore weresubjected to comparable growing conditions. Observations made three daysafter treatment are summarized in Table 3.v

TABLE 3 Physiological effects ACTIVE INGREDIENT PER PLANT Intensifiesmicrograms 50 micrograms, 100 micrograms 200 micrograms NoneDiethyl-ammonium acid maleate Diethyl-ammonium acid succinate r 6B, adhPL-mod bu; TS-mod rct 5B; adh PL-mod bu;

TS-mod ret bn; TS-mod rct I 813; adh PL-mod ha; 0B, 18; adh PL-irnzeu;

'lS-scv damaged 'lS-sev rot 813, IS: adh PL-mod 6B, 18; adh PL-frozcn;

bn; TS-sev rot TS-sev rct 1 Diethyl-ammonium 1B; adh PL-mod bu; 2B, 28;adh PL-mod 8B, 28; adh ILsev 9B,1S;adh PL'fi-ozcn;

acid malonate TS-lt ret' bn; TS-sev rot I ha; TS-sev rct TS-sev rctEXAMPLE 4 EXAMPLE 5 Four series of aqueous solutions of disodiuin3,6-endoxohexahydro-orthophthalate were prepared, each series consistingof four solutions having the following respective concentrations of thisactive ingredient: 0.001%, 0.0025%, 0.005%, and 0.01%.

One series of solutions contained no intensifier. Each of the otherthree series contained, in addition to the active ingredient, a constantamount (0.05%) of an intensifier. The respective intensifiers employedin preparing the respective series of solutions were diethylammoniurnacid maleate, diethylammonium acid succinate, and diethylammonium acidmalonate.

Thus the ratio of intensifier to active ingredient ranged from 5:1 to:1.

Separate groups of ten potted Dwarf Horticultural bean plants at thestage at which the first trifoliate leaf was still furled were dipped tothe first nodes into the respective test solutions of each series, andexcess solution was shaken off. Approximately 2 ml. of solution remainedon each Five series of aqueous solutions of disodium3,6-endoxohexahydro-orthophthalate were prepared, each series consistingof four solutions having the following respective concentrations of thisactive ingredient: 0.001%, 0.0025%, 0.005%, and 0.01%.

One series of solutions contained no intensifier. Each of the other fourseries contained, in addition to the active ingredient, a constantamount (0.05%) of an intensifier. The respective intensifiers employedin preparing the respective series of solutions were the acidtriethanolammonium salts of maleic acid, oxalic acid, succinic acid, andmalonic acid. 7

Thus the ratio of intensifier to active ingredient ranged from 5:1 to50:1.

Separate groups of eight potted Dwarf Horticultural bean plants at thestage at which the first trifoliate leaf was still furled were dipped tothe first nodes into the respective test solutions of each series, andexcess solution was shaken on". Approximately 2 ml. of solution retions.Observations made three days'lafter'treatf 1 ment are summarized inTable 4;

Tents 4 I Physiological effects ac'rrvn INGREDIENT PER PLANT:

After the test was com" '14 anhydrides probably contain non-ionized acidand/or anhydride in equilibrium with ionized material. Similarconsiderations might applyto some of the salts.-

5 The alkylammonium salts of 3,6-endoxohydroorthophthalic acids, such as,monoalkylammonium, dialkylammonium, or trialkylammonium saltspreferably have from 1 to 12 carbon atoms in each alkyl radical, thetotality of carbon atoms preferably beingnot more than 12. The alkanolammonium salts such as monoalkanolammonium, clialkanolammonium, ortrialkanolammonium preferably have from 2 to 3 carbon atoms in eachalkanol radical. The mixed alkylalkanolammonium salts such as monoalkylmonalkanolammonium, dialky1 monoalkanolammonium, or

100 micrograms 200'micrograms 713,15; adh PL-frozen;

sev ret. 1131 48; adh PL-irozen TS-sev ret -sev ret. 6B, 18; adhPL-frozen; 2B, 28; adh PL-frozen TS-sev ret. T

S-sev ret.

Intensifier 20 micrograms micrograms None PL-1tbn;TS-ltret; 4B, 2S; adhPL-mod bn; TS-mod ret Triethauolammon- 1B, 28; adh PL-mod 7B; adh PL-modhi1; ium acid maleatc bn; TS-mod ret TS-sev ret Triethanolammon-1S;adl1PL-ltbn;TS- 4B, 23; adh PL-mod ium acid oxalate mod ret bn;TS-mod ret Triethanolammon- 1B, 28; adh PL-mod 8B; TS-sev rot ium acidsuccinate bn; TS-mod ret Triethanolammon- 4B; adh PIrmOd bn; 8B; TS-sevret ium acid malonate TS-mod ret. V

EXAMPLE 6 Two series of aqueous solutions of disodium3.6-endoxohexahydro-orthophthalate were prepared, one without and onewith 5.05% of am-- monium acid fumarate, respectively, at the followingconcentrations of active ingredient: 0.005%, and 0.01%.

Separate groups of eight pottedDwarf Horticultural bean plants at thestage at which the first trifoliate leaf wasstill furled were dipped tothe first nodes into the respective test solu-- tions of each series,and the excess solution was shaken off. All plants were grown at thesame time and under the same conditions. 1

Observations made four days later were as follows:

The endoxo compounds are capable of existing in three separate anddistinct geometrically isomeric forms, namely, the exo-cis isomer, theendo-cis isomer, and the trans isomer, as defined by Woodward and Baer,Journal of the American Chemical Society, 70, 1161-1166. Of these threeisomers the exo-cis isomer is preferred in view of its outstandinglygreater activity. Furthermore, the exo-cis isomer can be prepared moreeconomically and conveniently. The endoxo ingredient in the foregoingexamples was of the exo-cis isomeric form.

When the endoxo ingredients are used in the form of the acids per seand/or their anhydrides, aqueous solutions containing such acids and/or5 monoalkyl dialkanolammonium ipreierably fh'ave from 1 to 4 carbonatoms'in each alkyl' radical and from 2 to 3 carbon atoms in, eachalkanol radical.

The neutral and 1 acid alkylamrnoniuin salts of the above-mentionedunsubstituted, openfrom 2 to 6 carbon atoms, such as monoalkylamniumsalts, preferably have from 1'tof4 carbon atoms in each alkyl radical.monium salts such as monoalkanolammonium, dialkanolammonium, ortrialkanolammonium preferably have from 2 to 3 canbon atoms in eachalkanol radical. The mixed alkylalkanolammonium salts such as monoalkylmonoalkanolammonium, dialkyl monoalkanolammonium; or monoalkyldialkanolammonium preferably have. from 5 1 to 4 carbon atoms in eachalkyl radical and from'2 to 3 carbon atoms in each alkanol radical. Thefollowing examples apply to both the 'ac'-;

tive ingredient and the intensifier.

Examples of monoalkylammonium salts are the monomethylammonium, n i u m,monopropylammonium, monobutylammonium, monoamylammonium,monohexylammonium, monoheptylammonium, monooctylammonium,monononylammonium, monodecylammonium, monoundecylammonium,monododecylammonium and similar monoalkylammonium' salts of such-acids.Y a 1 7 Examples of dialkylammonium salts are the dimethylammonium,diethylammonium, diproplyammonium, dibutylammonium, diamylammonium,dihexylammonium, methylethylammm n i u m, ethylpropylammonium,propylbutylammonium, butylamylammonium, amylhexylammonium,methylundecylammonium; and similar dialkylammonium salts of such acids.l

monium, dialkylammonium, or trialkylainmo- The alkanolam-.

monoethylammo- Examples of trialkylammonium salts are the 15trimethylammonium, triethylammonium, tri-- propylammonium,tributylammonium, methyldiethylammonium, ethyldipropylammonium,propyldibutylammonium, methyladiamylammonium, ethyldiamylammomum,methylethylpropylammonium, ethylpropylbutylammonium, and smile lar saltsof such acids.

Examples of monoalkanolammonium saltsar the monoethanolammonium,monopropanolammonium, and similar salts of such acids.

Examples of dialkanolammonium salts arethe diethanolammonium,dipropanolammonium,

ethanolpropanolammonium and similar salts of.

such acids.

Examples of trialkanolammonium salts are-the nium,dibutylethanolammonium, dimethylpropanolammonium,diethylpropanolammonium, di-' propylpropanolammonium,dibutylpropanolammonium, methylethylethanolammonium,methylethylpropanolammonium, ethylpropylethanolammonium,ethylpropylpropanolammonium, propylbutylethanolammonium,propylbutylpropanolammonium, and similar salts of such acids.

Examples of monoalkyl dialkanolammonium salts are themethyldiethanolammonium, ethyldiethanolammonium,propyldiethanolammonium, butyldiethanolammonium,methyldipropanolammonium, ethyldipropanolammonium',propyldipropanolammonium, butyldipropanolammonium,methylethanolpropanolammonium, ethylethanolpropanolammonium,propylethanolpropanolammonium, butylethanolpropanolammonium, and similarsalts of such acids.

As. pointed out above the salts contemplated include both the acid saltsand the neutral salts, and mixed salts, that is salts in which thecations are different. Y

The term plant as used herein is understood to. include all portions ofthe plant, such as the roots, stems, leaves, blossoms, seeds, andfruits.

Among the plants which defoliate naturally and'which may be defoliatedby the use of this invention, are for example, cotton, potatoes,tomatoes, and beans such as soy beans and lima beans.

Examples of noxious weeds against which my compositions may be used forherbicidal effects are bindweed, chickweed, cocklebur, mares tail,shepherds purse, broad-leaved plantain, wild lettuce, ragweed, spurge,dock, and wild carrot.

My new compositions are generally applicable as herbicides, such as inpre-emergencc or preplanting practices for the control of weeds, inpost-emergence treatment for control of weeds as to such useful crops towhich the formulation evidences only slight or no herbicidal action, andotherwise following agricultural practices.

From the foregoing it can be seen that the endoxo compounds used in thepractice of this invention, whether used as the acid or in equivalentform, are highly effective in regulating the growth characteristics ofviable or living plants,

16 and particularly of plants having vascular-systems, when used inadmixture with my intensifier; For example, the admixture may: beemployed to hasten defoliation ofplants which defoliatevnaturally, ormaybe employed to' t'ermihate the life cycle of plants, or may be' employedto retard the growing of seeds, or maybe" employed: to selectively stuntor terminate the growth-of certain unwanted plants to facilitate andfavor the growth ofwanted 'plantsyor may be employed toterminate thegrowth of vines in favor of, or to facilitate'harvesting of, thefruitszof'such vines, or maybe employed to 'stim ulate. root growth oncuttings, etc'. Otherap'- plications .of-the invention in the regulationof the growth characteristics ofiplants will 'occur to persons skilledin the art upon becoming familiar herewith.

Accordingly, it is to be understood that the particularv description isby way of illustration ,and that, the patent is intended to cover bysuitable expression in the claims whatever features of novelty reside inthe invention.

Iclaim: 1. A composition prepared for use as a plant response agentwhich comprises'a salt of an acid selected from the group consisting ofunsubstituted open-chain carbon-to-carbon linked di-.

carboxylic and tricarboxylic' acids having no greater unsaturation thana single olefinic link]- age and having from 2 to 6 carbon atoms, withat least one of the group consisting of ammonia, alkyl' amines, alkanolamines and mixed alkylalkanol amines; and a compound which when in thepresence of water, yields anions having the configuration CH 0 -t2;

in which R represents one of the group consist-' ing of the vinyleneradical and the ethylene radical. p

2. The composition of claim 1, and a wetting agent.

3.The composition of claim 1, and a humectant.

4. A composition prepared for use as a plant response agent comprising acompound which when in the presence of water yields anions of3,6-endoxohexahydro-orthophthalic acid; and a salt of an acid selectedfrom the group consisting of unsubstituted open-chain carbon-to-carbonlinked dicarboxylic and tricarboxylic acids having no greaterunsaturation than a single olefinic linkage and having from 2 to 6carbon atoms with at least one of the group consisting of ammonia, alkylamines, alkanol amines and mixed alkylalkanol amines.

5. The composition of claim 4 in which the anions are of the exo-cisisomeric form.

6. The composition of claim '5 in which said salt is an ammoniumoxalate.

'7. The composition of claim 6 in which said salt is ammonium oxalate.

8. A composition prepared for use as a plant response agent comprising acompound which when in the presence of water yields anions of 3,6 endoxo1,2,3,6 tetrahydro orthophthalic acid; and a salt of an acid selectedfrom the group consisting of unsubstituted, open-chain carbon-to-carbonlinked dicarboxylic and tricarboxylic acids having no greaterunsaturation than a single olefinic linkage and having from 2 to 6carbon atoms with at least one of the group consisting of ammonia, alkylamines, alkanol amines and mixed alkylalkanol amines.

9. The composition of claim 8 in which the anions are of the exo-cisisomeric form.

10. The composition of claim 9 in which said 1 salt is an ammoniumoxalate.

11. The composition of claim 10 in which said salt is ammonium oxalate.

12. A method for regulating the growth characteristics of a plant,comprising applying to said plant a plant response compositioncomprising a salt of an acid selected from the group consisting ofunsubstituted open-chain carbonto-carbon linked dicarboxylic andtricarboxylic acids having no greater unsaturation than a singleolefinic linkage and having from 2 to 6 carbon atoms with at least oneof the group consisting of ammonia, alkyl amines, alkanol amines andmixed alkylalkanol amines; and a compound which when in the presence ofwater yields anions having the configuration CH O mmiin which Yrepresents one of the group consisting of an unsatisfied valence and acation, and in which R represents one of the group consisting of thevinylene radical and the ethylene radical.

13. A method for inducing plant response in a living plant, comprisingapplying to said plant a composition comprising a compound which when inthe presence of water yields anions of 3,6-endoxohexahydro-orthophthalicacid, and a salt of an acid selected from the group consisting ofunsubstituted, open-chain carbon-to-carbon linked dicarboxylic andtricarboxylic acids having no greater unsaturation than a singleolefinic linkage and having from 2 to 6 carbon atoms with at least oneof the group consisting of ammonia, alkyl amines, alkanol amines andmixed alkylalkanol amines.

14. The method of claim 13 in which the anions are of exo-cis isomericform.

15. A method for inducing plant response in a living plant, comprisingapplying to said plant a composition comprising a compound which when inthe presence of water yields anions of 3,6 endoxo 1,2,3,6 tetrahydroorthophthalic acid, and a-salt of an acid selected from the groupconsisting of unsubstituted, open-chain carbon-to-carbon linkeddicarboxylic and tricarboxylic acids having no greater unsaturation thana single olefinic linkage and having from 2 to 6 carbon atoms with atleast one of the group consisting of ammonia, alkyl amines, alkanolamines and mixed alkylalkanol amines. 16. The method of claim 15 inwhich the anions are of the exo-cis isomeric form.

NATHANIEL TISCHLER.

No references cited.

1. A COMPOSITION PREPARED FOR USE AS A PLANT RESPONSE AGENT WHICHCOMPRISES A SALT OF AN ACID SELECTED FROM THE GROUP CONSISTING OFUNSUBSTITUTED OPEN-CHAIN CARBON-TO-CARBON LINKED DICARBOXYLIC ANDTRICARBOXYLIC ACIDS HAVING NO GREATER UNSATURATION THAN A SINGLEOLEFINIC LINKAGE AND HAVING FROM 2 TO 6 CARBON ATOMS, WITH AT LEAST ONEOF THE GROUP CONSISTING OF AMMONIA, ALKYL AMINES; ALKANOL AMINES ANDMIXED ALKYLALKANOL AMINES; AND A COMPOUND WHICH WHEN IN THE PRESENCE OFWATER YIELDS ANIONS HAVING THE CONFIGURATION